THERMODYNAMICS

(Lecture – 3)

The Three Laws of Thermodynamics

First law: Energy is conserved; it can be neither created nor destroyed.

Second law: In an isolated system, natural processes are spontaneous when they
lead to an increase in disorder, or entropy.

Third law: The entropy of a perfect crystal is zero when the temperature of the
crystal is equal to absolute zero (0 K).

First vs. Second Law

The First Law of Thermodynamics: The energy of the universe is constant -
energy is conserved.

This law tells us nothing about the spontaneity of physical and chemical
transformations consider the formation of water:

H2 (g) + ½O2 (g) H2O (l) ΔHfo = -286 kJ mol-1

Using the first law, it is easy to calculate ΔU and ΔH associated with this
spontaneous reaction. We can also calculate ΔU and ΔH for the reverse reaction,
which we know does not occur spontaneously. Neither the sign nor the magnitude
of ∆U and ∆H tell us which way the reaction will go - however, we can get this
information from the Second Law of Thermodynamics.
The Second Law: Entropy
 The universe tends towards more random, disorganized states.
 Our way of quantitating the disorder and randomized motion in one state
versus another is a state function called entropy: increasing entropy means
increasing disorder and randomized motion.
 The law used to identify spontaneous change, and can be quantified in terms
of a state function known as entropy.
 Entropy is a state function that describes the molecular disorder of the
system.
 The entropy of an isolated system increases in the course of spontaneous
change,
ΔStotal > 0
where Stotal is the total entropy of a system and its surroundings. i.e.,
ΔStotal = ΔSsys + ΔSsur
 Entropy is a measure of molecular disorder in a system, letting us assess
whether one state is accessible from another via spontaneous change. In a
spontaneous process,
∆S = Sfinal – Sinitial > 0

Spontaneous Process
 A spontaneous process is one that occurs on its own without any outside
assistance in a definite direction.
 A gas will expand into a vacuum, (the expansion is spontaneous) but the
process will never reverse itself.
A nail will rust but a rusty nail will never become shiny.
Fe (s) + O2 (g) Fe3O4 (s)
 Process that are spontaneous in one direction are nonspontaneous in the
opposite direction.
Entropy Change in Reversible and Irreversible Process
“In general, any irreversible process results in an overall increase in entropy
whereas a reversible process results in no overall change in entropy.” This
general statement is an alternative expression of the Second Law of
thermodynamics.

Reversible process: ∆Stotal = ∆Ssystem + ∆Ssurrounding = 0

Irreversible process ∆Stotal = ∆Ssystem + ∆Ssurrounding > 0

Entropy usually increases in the following situations

 A reaction in which a molecule is broken into two or more smaller
molecules
 A reaction in which there is an increase in moles of gas
 A process in which a solid changes to a liquid or gas
 A process in which a liquid changes to a gas

Thermodynamic Definition of Entropy

If an infinitesimal change in entropy is dS, and this can occur as a result of a
chemical or physical process, then the thermodynamic definition of entropy:
For a measurable change between two states i and f:

Or,

Problem

Has entropy increased (∆S > 0) or decreased (∆S < 0) in the following processes?

a. C6H12O6 (s) = 2C2H5OH (l) + CO2 (g)

b. NH3 (g) + CO2 (g) = NH2CONH2 (aq) +H2O (l)

c. CO (g) + H2O (g) = CO2 (g) + H2 (g)

d. HCl (g) + NH3(g) = NH4Cl (s)

e. SO2 (g) + O2 (g) = SO3 (g)

The third law of thermodynamics
At absolute zero, or when T = 0 K, all energy of thermal motion has been
quenched, and all atoms or ions in a perfect crystalline lattice are in a perfect
continuous array.

 No spatial disorder
 No thermal motion
 Entropy is zero, there is only one way of arranging the molecules

A system cannot actually reach absolute zero – everything has some internal
energy!

The third law of thermodynamics can be stated as

“The entropy of a pure crystalline substance at absolute zero is 0.”

Entropy Change in the Universe

The universe is composed of the system & surroundings.

Therefore,

∆Suniverse = ∆Ssystem + ∆Ssurroundings

Since ∆Ssurroundings = - qsystem/T and qsystem = ∆Hsystem
∆Suniverse = ∆Ssystem + (- ∆Hsystem)/T
Multiplying both sides by - T,

- T∆Suniverse = ∆Hsystem - T∆Ssystem

- T∆Suniverse is defined as Gibbs Free Energy, ∆G.

∆G = ∆Hsystem - T∆Ssystem

 When ∆Suniverse is positive ∆G is negative, the forward reaction is

spontaneous.
 When ∆Suniverse is negative ∆G is positive, the reaction is spontaneous in
reverse direction.
 If ∆G = 0, the reaction is at equilibrium.

The fundamental equation

The first law: dU = dq + dw

For a reversible change in a system with constant composition and no non-

expansion work: dwrev = -pdv & dqrev = TdS

Therefore,
dU = TdS – pdv

This is the fundamental equation of thermodynamics.

Calculations Involving ∆G
The Gibbs Free Energy ∆G◦ can be calculated from thermodynamic tables using

∆rG◦ = Σ n∆Gf◦ (products) – Σ m∆Gf◦ (reactants)

or ∆G° = ∆H◦ - T∆S◦

Equations:

The Gibbs free energy of a system is defined as, G = H – TS

The change in the Gibbs free energy of the system, ΔG = ΔH - Δ(TS)

If the reaction is run at constant temperature, ΔG = ΔH - TΔS

The standard-state free energy ΔG◦ = ΔH◦ - TΔS◦

Problem

For the reaction, N2 (g) + 3H2 (g) 2NH3 (g)

Compound ΔHf◦ (kJ/mol) S◦ (J/mol-K)

N2(g) 0 191.61

H2(g) 0 130.68

NH3(g) -46.11 192.45

Here,

ΔH◦ = ΔHf◦(products) - ΔHf◦ (reactants)

= (2 x -46.11) – (0 + 0)

= -92.22 KJ/mol

ΔS◦ = (2 x 192.45) – (191.61 + 3 x 130.68)

 = -198.75 J/mol-K

Will this reaction occur spontaneously at 25◦C?

 The enthalpy of reaction is favorable ΔH° is exothermic (ΔH° < 0)

ΔH° = - 92.22 kJ (favorable)
 The entropy of reaction is unfavorable, however, because there is a
significant increase in the order of the system, when N2 and H2 combine to
form NH3
ΔS° = - 198.75 J/K (unfavorable)

Now at 25◦C i.e. (273.15+25)K or, 298.15K

ΔG◦ = ΔH◦ - TΔS◦

= - 92,220 J - (298.15 K x -198.75 J/K)

= - 92,220 J + 59,260 J

ΔG◦ = - 32,960 J = - 32.96 kJ

Here, ΔG at 25◦C (or, ∆G◦) is negative, so the forward reaction will occur
spontaneously.

** If ΔG is negative in a reaction, the process is called to be exergonic, and

will occur spontaneously. If ΔG is positive in a reaction, the process is called to
be endergonic, and forward reaction will NOT occur spontaneously. An
endergonic process can only occur when it is pulled or pushed by an exergonic
process.

Gibbs Energy, ΔG, under any nonstandard condition, can be calculated from ∆G◦:

∆G = ∆G◦ + RT lnQ

Here, Q is the reaction quotient.

For a reaction A B, Q = pB / pA, and the value ranges from 0 to .

At equilibrium, ∆G = 0 (the reaction will not go in any direction), and Q = K

(equilibrium constant). Therefore,

∆G◦ = -RT lnK (Thermodynamic equilibrium constant)

From ∆G, we can therefore tell if a chemical reaction will proceed at forward
direction, at reverse direction, or if the system is at equilibrium.

Figure: ∆G is the slope of the graph of the Gibbs

Energy plotted against the extent of reaction
(change in number of moles of reactant or
product). At a point when ∆G < 0, the net
reaction will be at forward direction. At a point
when ∆G > 0, the reverse reaction will prevail. At
equilibrium, ∆G = 0

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Thermodynamics Lecture – 3
Arif Rafid, Lecturer, Department of Pharmacy, Southeast University
Course: Physical Pharmacy – II

References
1. Class Lectures, Dr. Ozge Gunaydin-Sen, Assistant Professor of Physical Chemistry,
LU, Texas, USA
2. Essentials of Physical Chemistry, Ed. 2004-2005, BS Bahl, GD Tuli, A Bahl